Perfluoroalkyl sulfonamides and carboxamides



United States Patent M 3,450,755 PERFLUOROALKYL SULFONAMIDES ANDCARBOXAMIDES Arthur H. Ahlbrecht, Dellwood, Minn., assignor to 3,450,755Patented June 17, 1969 groups. The compounds of the invention are thusvaluable intermediates.

The novel primary amines of the invention may be prepared by severalmethods. Some procedures are Widely Minnesota Mining and ManufacturingCompany 5 applicable and others are of more limited applicability St.Paul, Minn., a corporation of Delaware as W111 become pp No Drawing.Continuation-impart of application Ser. No. The compounds of theinvention may be prepared 350,563, Mar. 9, 1964. This application Feb.23, 1967, (Gabriel synthesis) from the N-alkyl perfluoroalkane-sul- Ser.No. 617,796 fonamide or -carbonamide by condensation of the alkali Illt-(3070145772; (309(13/48 metal salt with N-(omega-haloalkyl) phthalimidesfol- 260 556 2 Chums lowed by cleavage, for example, with hydrazine.Another useful method is the ammonolysis of arenesulfonate esters ofcarbinols corresponding to the desired primary amine. ABSTRACT OF THEDISCLOSURE The ammes of the invention react Wlth the reactive 15 groupsof epoxy resins, lsocyanates and the llke in form- N-alkyl,N-omega(primary)aminoalkyl perfiuoroalkaneing coatings for conferringoleophobicity on surfaces of sulfonamides and -carbonamides are providedand are textiles, plastics, leather, metal, glass and ceramics anduseful, inter alia, as epoxy resin curing agents to form further formpolymerizable acrylamides. They are thus coatings. valuableintermediates in treatments of surfaces where alteration of propertiesis desired.

The following examples further illustrate compounds of the invention.This application is a continuation-in-part of my copending applicationSer. No. 350,563 filed Mar. 9, 1964, EXAMPLE 1 now l i w The sodium saltof N-ethyl perfiuorooctanesulfonamide ThlS invention relates to newprimary amrnes and paris prepared from the amide and sodium hydroxide intlcllfllarly Ngomegaijmmoalkyl perfluoroalkane' acetone solution andbrought to dryness. A vessel equipped i g' a bonaml k h for reflux andstirring is charged with 252 g. of the dry t Dug uprocar E are nown amsodium salt, 127 g. of N-(ti-bromoethyl)phthalimide, 10

neutral and basic functions, e.g. carboxyllc acids as deof Sodiumcarbonate, 10 g of potassium iodide and 500 q example q Patent 2809090and m1. of acetone. The resulting solution is stirred and resulfomcaclds as described in Brice and Trott, U.S. Patent fluxed for 48 hourscooled and filtered to remove the 3 1 3 1 jgfif if g g. g g g gg fprecipitate of sodium bromide. The filtrate is evaporated brec t an d fgand finally distilled under reduced pressure: N-(N'-ethylternary amme las e m y atent ,B-perfluorooctanesulfonamidoethyl)phthalimide distillsat 2,759,019 and prlmary amines as described 1n Husted to 1 C at 03mm'Hg pressure and Ahlbrecht Patent. 4 It appears h A solution of 104 g.of the above phthalimide and 50 fluorocarbons havmg basic Properties theactwe g. of percent hydrazine hydrate in g. of ethanol sg g z gg igg gigggigf fi izg g g igg gz 40 is refluxed for four hours and cooled. Theprecipitate of 0 311 or more atoms have not her etofore been readilphthalazme is removedby fiitrfltlon and the filtra-t6 1s M y evaporatedand the residue distilled. The product is 56 aval a} g. ofN-ethyl-N-fi-aminoethyl perfluorooctanesulfonamide It 1s one ob ect ofthis invention to provide primary boiling at to at 025 mm Hg Pressure.havmg Calculated r01- c F n so N z 4.91% N. Found:

It is a furthe ob ect of th1s lnventlon to provide fluoro- 45 478%carbonlermmatid amlpe curmg agents for epoxy i The hydrochloride isprepared by evaporation of an Addmona! objects W111 become apparent fromthe ethanolic solution of the above amine and hydrochloric closurehereln. acid In accordance with these and other objects of the inven-Calculated for c F H N 5 86% 4 63% N tion it has been found thatfluorocarbon terminated 0 Found: 625% 22, 2 pnmary ammes of the formulaThe amine is reacted with acrylyl chloride in ether R1 and N-ethylN-B-acrylamidoethyl perfluorooctanesulfonamide is obtained as a Whitesolid melting at 124 to R"'Q N RZNH2 5 126 C. This acrylamidepolymerizes under free radical wherein Rf is perfluoroalkyl of 1 to 18carbon atoms, R 0 Condltlons' is saturated alkyl of 1 to about 6 carbonatoms, R is EXAMPLE 2 bridging alkylene of 2 to 13 carbon atoms and Q isS0 or C0 are reactive with epoxy resins and isocyanates to When theprocedure of Example 1 is repeated employgive polymers possessingfluorinated groups. They may be 60 ing the sodium salts of theperfluoroalkanesulfonamides converted to di-amines by reaction withcyanuric chloride and the omega haloalkylphthalimides set forth in thefolfollowed by conversion of two further chlorines to amino lowingtable, the indicated amines are obtained.

TABLE 1 N-haloalkyl of Sulionamide phthalimide Product amineCFBSO2N(CH3)H B1(CH2)11 CFa O2N(CHa)-(CH2)11NH2 C4F9SO2N(C2H5)HBrC2H4-.. C4F9SO2N(C2H5)CzH4NH2 C1zF2sSO2N(C2Hs)H. BrCs 1eC12F25SO2N(C2H5)(CH2)3NH2 CaF 7SO2N(CaH13)H B1C2H4 CaFnSOzN 0H C2H4- 3EXAMPLE 3 A shaking autoclave adapted to withstand pressures to 2,000p.s.i. and fitted with rupture disc is charged with 207 parts (0.284mole) of N-ethyl perfluorooctanesulfonamidoethyl benzene sulfonate(prepared from the carbinol and benzene sulfonyl chloride andtriethylamine in acetone solution), 300 parts by volume of absoluteethanol and 80 parts (4.7 moles) of liquid ammonia and then closed. Thetemperature is raised while shaking to 120 to 125 C. and maintained forsix hours. The autoclave is then cooled and vented. The reaction mixtureis worked up by adding an anhydrous ethanolic solution of 0.284 mole ofpotassium hydroxide and, after stirring for about 10 minutes, theprecipitate of potassium. benzene sulfonate is collected and thefiltrate and washes evaporated under reduced pressure. The crude oilyproduct is taken up in absolute ether (400 parts by volume) and thesolution tfiltered. The product is obtained as an oil boiling at 104 C.at 0.17 mm. Hg pressure by evaporation of the ether and is identical tothe product of Example 1. It is converted to the hydrochloride bypassing hydrogen chloride into the dry etheral solution.

EXAMPLE 4 When the above procedure is repeated employing sulfonateesters of the N-alkyl perfluoroalkanesulfonamido alkanols shown in thefollowing table, the amines indicated are obtained. The alkanols areavailable by the procedure of Ahlbrecht and Brown, U.'S. Patent2,803,656, and extension of the procedure thereof to otherperfluoroalkane sulfonyl fluorides available by the process of Brice andTrott, US. Patent 2,732,298.

Table 2 N-alkylperfluoroalkanesulfonamido alkanol:

Product amine:

EXAMPLE 5 N-methyl perfluorocapramidoethanol,

(n =1.355; from methyl perfluorocaproate and N- methyl ethanol amine,generally as described in Diesslin et al. US. Patent 2,067,011 foramides) is converted to the benzene sulfonate by stirring 23.75 parts in30 parts of methylene chloride and 5.55 parts of triethylamine at 20 to25 C. while adding 8.85 parts of benzene sulfonyl chloride. Stirring iscontinued for 2.5 hours, 60 parts by volume of water at C. are addedand, after separation of layers, the organic layer is further 'Washedwith water and evaporated to a residue. The product residue is 29.5parts of the benzene sulfonate ester:

CgFg 020 1 The total ester (29.5 parts) is dissolved in 60 parts ofabsolute ethanol and 7.5 parts of anhydrous ammonia are introduced. Themixture is heated at -105 C. for 4 75 hours in a stainless steelautoclave as in Example 3 and then cooled. Sufiicient solid potassiumhydroxide (3.1 parts, 0.055 mole) is added to the reaction mixture toneutralize the sulfonic acid. The potassium salt precipitates and iscollected. The solution is brought to a residue and taken up in acetoneto precipitate more of the potassium salt. Evaporation gives C F CON(CH)C H NH as a semi-pasty solid at room temperature; n =1.375.

The amine is reacted with an epoxy resin to give an oil repellentcoating by an essentially conventional method which assures homogeneityof coating.

To a boiling solution of 5 parts of epoxy resin with equivalent weightof 1900 (for example, Epon 1007) in 20 parts of C H 'OC H OCOCH is addedone part of the above amine (equivalent weight about 640). The solutionis boiled for about 10 minutes, adding further solvent as needed, toprereact the fluorinated material with epoxy resin. A portion of thesolution is coated on a glass microscope slide and dried at C. for 15minutes. The coating is colorless, clear and hard. The coating isapplied to other surfaces as desired by the same procedure. The contactangle of hexadecane measured against the coating is about 79. The anglemeasured against a coating of the epoxy resin cured with conventionalnon-fluorinated amine is about 0. This demonstrates the oleophobiccharacter of the coating produced.

This same procedure is used to produce oleophobic coatings from otheramines of the invention with similar results.

EXAMPLE 6 When the procedure of Example 5 is repeated using sulfonateesters of other carbonamidoalkanols the correspondingcarbonamidoalkylamines are obtained as indicated in the following table.

Carbonamidoalkanol:

Product carbonamidoalkyl amine:

What is claimed is: 1. A perfluoroalkanesulfonamidohydrocarbon amine ofthe formula wherein R is saturated perfluoroalkyl of 1 to 18 carbonatoms, R is saturated alkyl of 1 to about 6 carbon atoms,

5 R is bridging alkylene of 2 to 13 carbon atoms and Q is a member ofthe group of divalent groups SO and CO.

2. N-ethylperfluorooctanesulfonamidoethyl amine.

References Cited UNITED STATES PATENTS 9/1965 Guenthner 260-79.3

FOREIGN PATENTS 732,631 4/1966 Canada.

HENRY R. J'ILES, Primar'y Examiner. 5 H. I. MOATZ, Assistant Examiner.

US. Cl. X.R.

mg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 3, 5 ,755 mtJune 17, 1969 Arthur H. Ahlhrecht Patent No Inventofl e) It 1e certifiedthat error eppeere in the ebove-identified petent end that eetd LetterePetent ere hereby corrected ee ehm below:

Column 1, line +5, "furthe" should read --further-- Colum: line 71, "C Fshould read --C F Column 4, line 7,

3 "21 F should read --C F SIGNED ANU SEALED OCT 21 w EdwerdlFletcherJx.MngOfficer Gonmissioner of Patents

